Fluorescent stilbyl ditriazole



FLUORESCENT STILBYL DITRIAZOLE COMPOUNDS Reinhard Zweidler, Basel, andErnst Keller, Binningen,

Switzerland, assignors to J. R. Geigy A. G., Basel, Switzerland, a Swissfirm No Drawing. Application March 17, 1955, Serial No. 495,042

Claims priority, application Switzerland March 19, 1954 6 Claims. (Cl.260-308) Fluorescent stilbyl ditriazole compounds which are fast tochlorine are described in the copending application, Serial No. 495,041,filed on even date herewith, which are obtained, among other ways, bycoupling diazotised 4-aminostilbene-Z-sulphonic acids with an m-diaminocompound of the benzene series which can be coupled twice to form theo-aminoazo dyestuff, oxidising this to form the corresponding2-(stilbyl-4')-5-amino-1.2.3- benztriazole-2-sulphonic acid, againcoupling with an aromatic diazo compound and oxidising to form theditriazole. Such stilbyl ditriazole compounds fluoresce in ultra-violetlight green-blue and, because of their substantivity, they are suitablefor the optical brightening of cellulose materia.

On further work being done on the subject matter of this invention ithas been found that valuable, greenishblue fluorescing substantivestilbyl ditriazole compounds are also obtained if the2-(stilbyl-4')-5-amino-1.2.3- benztriaZole-2'-sulphonic acids which areoften described in the copending application as intermediate productsare further diazotised, coupled with an azo component coupling in theo-position to a primary amino group and then oxidising the o-aminoazodyestutf formed by methods known per se to form the ditriazole compound.The diazo component can be substituted in the 6-position, for example itcan contain halogen, a methyl, alkoxy, aryloxy, a sulphonic acid or amodfied sulphonyl group.

Examples of azo components coupling in the o-posi-tion to a primaryamino group are; 1-amino-3-alkoxy-4-methyl benzene,l-amino3.4-dialkoxybenzene, 1.3-diaminoben- States Patent "ice 2,784,197Patented Mar. 5, 19 57 The new stilbyl ditriazole compounds correspondto the general Formulal and are free from groups imparting dyestuffcharacteristics, i. e. chromophores such as nitro, azo and azoxy groupsand aromatically bound hydroxy and amino groups. In this formula:

A represents a phenyl radical possibly substituted by simplesubstituents such as halogen, alkyl or alkoxy groups,

B represents an o-phenylene or o-naphthylene radical which can possiblybe substituted by halogen, alkyl, alkoxy, aryloxy, carboxylic acid,sulphonic acid or modified sulphonyl groups,

X represents hydrogen, or a substituent like halogen, an alkyl, alkoxy,aryloxy, the carboxyl, the sulphonic acid or a modified sulphonyl group.

In the form of their water soluble alkali metal salts, the new stilbylditriazole compounds are yellow-brown powders which produce colourlessto weakly yellowish coloured aqueous solutions and, in aqueous solutionsor when adsorbed on to more or less white substrata such as, e. g.cellulose fibres, they have a strong green-blue fluorescence inultra-violet light. Even from very diluted aqueous solutions which cancontain salts, soaps, synthetic Washing agents or oxidising bleachingagents, they draw on to cellulose fibres and, even in a very slightcontent, by the optical compensation of the yellowish appearance throughthe green-blue fluoresence light, they bring about a strong brighteningin daylight. Also, in a very slight content and fine distribution, theylend to other more or less white substrata, such as for example starch,soap, synthetic washing agents, a better white appearance in daylight.

The following examples illustrate the invention without limiting it inany way. Where not otherwise stated, the parts are given as parts byweight and the temperatures are in degrees centigrade. The relationshipof parts by weight to parts by volume is as that of kilogrammes tolitres.

EXAMPLE 1 lene, 6-bromo-2-aminonaphthalene, 6- or 7-methoxy-2-aminonaphthalene, 2-aminonaphthalene-3-carboxylic acid,2-aminonaphthalene-l-, -5-, -6-, or -7-sulphonic acid, 2-aminonaphthalene-3.6- or -5.7-disulphonic acid.

It is of advantage to use ammoniacal copper sulphate or alkali metalhypochlorites as oxidising agents.

39.2 parts of S-amino-Z-(stilbyl-l' -1.2.3-benztriazo 1e- 2'-su1phonicacid are dissolved hot in 200 parts of dimethyl formamide, the solutionis cooled somewhat, 200

parts of ice and about a 30% aqueous solution of 6.9 parts of sodiumnitrite are added. The mixture is indirectly diazotiscdat a temperatureof 8-10 by pouring it into a mixture of Water, ice and 25 parts ofconcen trated hydrochloric acid. After stirring for a short time, thediazo suspension obtained is coupled at a temperature of 12-l5 with anaqueous solution of the disodium salt of 30.3 parts of2-aminonaphthalene-S.7-disulphonic acid and the mineral acid is bufferedby the addition of 25 parts of crystallised sodium acetate. Oncompletion of the coupling, the dyestulf is completely salted out by theaddition of sodium chloride, filtered oil? and washed. The

damp o-aminoazo dyestuft with the addition of caustic pension obtainedis coupled at a temperature of 12-15" soda lye is dissolved in hot waterwith a phenolphthalein with an aqueous solution of the disodium salt of30.3 alkaline reaction and then about 100-120 parts of a parts ofZ-aminonaphthalene-5.7-disulphonic acid with the sodium hypochloritesolution containing 17% of active addition of 25 parts of crystallisedsodium acetate. On chlorine are added dropwise within 15 minutes at atemcompletion of the coupling, the dyestutf is salted out, perature of30-35". On completion of the dropwise adfiltered off and washed. Thedamp o-aminoazo dyestulf dition, the temperature is raised within 1 hourto 80-85 is then dissolved hot in hot water with the addition of duringwhich time starch/iodide paper should always caustic soda lye untilthere is phenolphthalein reaction and show an excess of active chlorine.The ditriazole comoxidised at a temperature of 35-40 as described inExpound is then completely salted out with sodium chloride, ample l with100-120 parts of a sodium hypochlorite filtered off and washed. It isfurther purified by dissolvsolution to form the ditriazole compound. Itis then puriing the damp raw product in hot water, adding 3-8 partsfied. The ditriazole compound of the above formula is of hydrosulphiteat a temperature of 92-97 to decoma yellow powder which dissolves wellin water. The prodpose oxidation products and filtering the solution hotwith net is a valuable brightening agent for cellulose fibres; theaddition of active charcoal. The product is again the brighteningeffects obtained therewith are distinguished salted out, filtered off,washed and dried in the vacuum. by their excellent fastness to chlorine.

EXAMPLE/3 no. NL LBN The ditriazole compound obtained of the aboveformula 47.2 parts of 5-amino-2-(stilby1-4')-1.2.3-benztriazoleis ayellow powder; diluted solutions thereof are weakly 2.6-disulphonic acidare indirectly diazotised as described yellowish coloured. Because ofits substantivity, the in Example 2 and then the diazo suspensionobtained is compound draws on to cellulose fibres even from diluted 30coupled at a temperature of 12-15 with an aqueous sosolutions and lendsthese fibres a white shading in daylution of 13.7 parts of1-amino-3-methoxy-4-methyllight. It can also be used as a brighteningagent for benzene in 11 parts of concentrated hydrochloric acid soappowders and synthetic washing agents. On more or and 200 parts of water.25 parts of crystallised sodium less white substrata, for example oncellulose fibres, it tat r gradually added during the coupling, 011 hasexcellent fastness to chlorine and very good fastness complefign of hcoupling h dyggtufi i lt d to light. The o-aminoazo dyestuff can also beoxidised filt d ff and Washed. The damp Q-amin0azo dy t fl withcuprammPnium sulphate by dissolving h is dissolved with 25 parts of 25%ammonia in hot water, dyesmfi f 25 Parts of 25 ammoma water a mixture of60 parts of crystallised copper sulphate in and thenladding a mlxmre Of60 parts of crystaulsed 240 parts of water and 120 parts of 25% ammoniais Per sullihate i i s. Water and 120 Partsf 3? 40 added and the wholeis kept at a temperature of 92-97 19 32 p 0 i ig i g g 0 g until thedyestuff is completely oxidised. The raw ditril e yes u 15 Comp e e y 0I we n comp n azole compound is then salted out, filtered off and of theoxidation, the ditriazole compound is completely salted out, filteredoff and washed. It is further purified Washed The product 15 furtherpunfied by agam (115' by dissolving in hot Water, removing the copper inthe Solvmg m C removmg thefoppef the 9 of form of copper sulphide withsodium sulphide and de- PP suiphlde by treatmePt w spcdmm sul'phlde fcomposing reduceable oxidation products with sodium hydecomposingreduceable {JXldatlOIl Products )Vlth 805mm drosulphite. The compound isthen salted out and dried h Ph The dltllazole Compound 15 a Yellow inthe vacuum. The compound obtained is identical to powder and can be usedfor the brightening of cellulose the product described above and has thesame properfibres, soap powders and synthetic Washing agents. The ties.brightening effects obtained therewith are distinguished EXAMPLE 2SOsI-I 80:11 47.2 parts of 5-amino-2-(stilbyl-4')-1.2.3-benztriazolebyexcellent fastness to chlorine and first-rate fastness to2'.6-disu1phonic acid in the form of the sodium salt are light.dissolved in 2000 parts of hot water, an aqueous solu- If in the aboveexample, the 1-amino-3-methoxy-4- tion of 6.9 parts of sodium nitrite isadded and the whole methylbenzene is replaced by 15.3 parts ofLamina-3.4- is indirectly diazotised at a temperature of 8-10 with 25dimethoxybenzene then a ditriazole compound of the parts of concentratedhydrochloric acid. The diazo susformula:

ti... t isobtained.-

5 6 This compound is also a valuable brightening agent. liquorcontaining 3 g. of curd soap, 2 g. of sodium carbon Compared with thatof the above named compound, its a an 0. 02 gof. the ditriazole compoundObtained fluorescence is shifted more towards the long wave range.according to Example 2 P The goods are lhcn Adsorbed on to cellulosefibres it also has good fastness Tined and dried- A dazzling White Washis Obtained to chlorine and light 5 which has no unpleasant reddishtinge.

The following compounds can be produced by the methods described inExamples l--4. They also have EXAMPLE 4 similar properties.

Table I 4 5 C 3 Hsio. NN-i 'i q I -cn=on' N 308E 47.2 parts of5-amino-2-(stilbyl-4)-1.2.3-benztriazole- 2'.6-disulphonic acid areindirectly diazotised as described \T Z Fluorescence in Example 2 andthe diazo suspension obtained is then i T f fi fl coupled at atemperature of 12-15 with an aqueous a-1 solution of 10.8 parts of1.3-diaminobenzene in 200 parts of water with the addition of parts ofcrystallised so- 5 :g

dium acetate. On completion of the coupling, the dyei ee uestuff isisolated, dissolved in hot water with the addition I382? 5 353 31;

of 25 parts of 25% ammonia, a mixture of 60 parts 2; :gggg 5g ofcrystallised copper sulphate in 240 parts of water and 4:8 -SO3Hblue-green.

120 parts of 25% ammonia is added and the whole is kept at a temperatureof 9297 until the dyestufi is complete- Table 2 1y oxidised. The rawditriazole compound is completely 3 4 Y salted out, filtered ofi,de-coppered with excess sodium OCH=CH :2

sulphide and purified with sodium hydrosulphite to re- I move reduceableoxidation products. The damp amino- 35 E30, C 6 z ditriazole compound isthen dissolved in water, indirectly diazotised, isolated and the diazocompound is warmed with dimethyl formamide, during which the diazo groupis replaced by hydrogen while splitting off nitrogen. Fluores- Afterfurther purification, the ditriazole of the above 40 X: Y: Z: g

formula is obtained as a yellow powder. The compound t;

can be used for the brightening of cellulose fibres, soap g'lhtm powdersand synthetic washing agents Thebrighten- 5 4 gremblm mg effectsobtained therewith are distinguished by ex- 5 -01 4 OCH3 green.

cellent fastness to chlorine and first-rate fastness to light. 2 :g om i8285; gree i -gine.

A compound with a similar effect is obtained if in the 5 a green 5 S 03HH green-blue. above example the 1.3-d1ammobenzene is replaced by 5 s0,11H Do, 12.2 parts of 1.3-diamino-4-methylbenzene and pro- 4 NH CO CH=greencedure analogous to that described above is followed. 17.....-"'SQIH 5 -OH= 4 NH-OO-C Do.

The ditriazole compound of *the formula: t

a... \vL lii is a yellow powder and is an interesting brightening agent-What we claim is: for cellulose fibres, soap powders and syntheticwashing 1. A stilbyl distriazole compound corresponding to the agents.general formula:

EXAMPLE 5 White cotton poplin is treated in a bath (liquor ratio 1:50)for 15 minutes at a temperature of with 0.005% (calculated on the weightof the fibres) of the N ditriazole compound obtained according toExample 2, g I\ the treatment being performed in the presence of 5% 3Glaubers salt (calculated on the weight of the fibres). N

After rinsing and drying, the material treated has a considerably morewhite appearance than before treatment.

EXAMPI "B 6 wherein A represents phenyl, B represents a member 1 part ofwhite wash, e. g. pillow cases, sheets etc., are selected from the groupconsisting of o-phenylene, halowashed in the usual way at -100 in 10parts of a wash geno-o-phenylene, lower alkyl-o-phenylene, lower alkoxy-2,784,197 '7 S o-phenylene, lower alkyl, lower alkoxy-o-phenylenmlower sall op calr g flg ag 'fi y ri l e dialkoxy-o-phenylene, lowerdialkoxy-o-phenylene, aroylc p f the formula! amino-o-phenylene,sulpho-o-phenylene, 1.2-naphthy1ene,

sulp'ho ll-naphthylen and disulpho f 1.2 Q naphthylene O r radicals, andX represents a member selected from the 5 A \b/ group consisting of H,CH3, -O CH3, CI and SOsH. H O

2. A stilbyl ditriazole compound of tlge formula A H H80: Q 05H 3. Astilbyl ditfiazole compound of the formula:

5. A stilbyl ditriazole compound of the formula:

GH=GH N N NOW,

' SOaH References Cited in the file of this patent UNITED STATES PATENTS2,385,862 Keller 06L 2, 1945 2,462,405 Keller et a1 Feb. 22, 19492,467,262 Knight Apr. 12, 1949 2,668,777 Gold et a1. Feb. 9, 19542,713,057 Zweidler et al. July 12, 1955 FOREIGN PATENTS v 1,054,820France; Got. 14, 1953

1. A STILBYL DISTRIAZOLE COMPOUND CORRESPONDING TO THE GENERAL FORMULA: